Fabrication of electrospun nanofibres is the glittering area of research because of their flexible characteristics and numerous applications in almost all walks of life and technology. Poly(methyl methacrylate) (PMMA) is one of the significant and interested synthetic polymers in the recent research because of their characteristic properties like higher environmental stability, resistance to attack by moulds and enzymes, commercial availability, easiness to handle, etc. In the present study, pristine PMMA nanofibres with diameters of 60-150 nm with 109 nm as the most distributed one are prepared by an electrospinning method using a binary solvent mixture. An enhancement in the intensity of visible photoluminescence emission is observed in PMMA nanofibres embedded with samarium and neodymium β-diketonate complexes. The morphological incorporation of samarium and neodymium β-diketonate complexes in PMMA nanofibres and material composition of the samples are examined by high resolution electron microscopy analyses. The amorphous nature and molecular bonding of pure PMMA nanofibres and incorporated fibre complexes are elucidated through structural and molecular analyses. The supreme optical absorptions and reemissions of samarium and neodymium β-diketonate complexes embedded in the pure PMMA fibre sample in the visible region indicate not only their application in lighting or display devices, but also as active materials in organic light emitting diodes for new era curved/rolled display devices.